TW201813984A - 氟聚合物及包含氟聚合物（ｉｉｉ）的膜 - Google Patents

氟聚合物及包含氟聚合物（ｉｉｉ）的膜 Download PDF

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TW201813984A
TW201813984A TW106126566A TW106126566A TW201813984A TW 201813984 A TW201813984 A TW 201813984A TW 106126566 A TW106126566 A TW 106126566A TW 106126566 A TW106126566 A TW 106126566A TW 201813984 A TW201813984 A TW 201813984A
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fluoropolymer
porous
mixture
porous membrane
film
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法蘭克 歐可薩 昂葉毛瓦
哈多 哈森 阿義特
閻 拉不奇
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帷幕公司
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Abstract

本發明揭示具有低CWST值之氟聚合物及由該等氟聚合物製備之多孔膜。該氟聚合物由式A-X-CH2-B之聚合單體單元構成，其中A為C6F13-(CH2)2，X為O或S，且B為乙烯基苯基，且該氟聚合物具有至少100Kd之重量平均分子量(Mw)及/或至少33℃共聚物之玻璃轉移溫度。該等多孔膜適合於將多種流體脫氣。

Description

氟聚合物及包含氟聚合物(III)的膜
正考慮將包含氟聚合物之膜用於過濾多種流體，例如用於移除分散於流體中之氣體。一些此等膜之特徵為低表面能值或臨界潤濕表面張力(CWST)值及/或對有機溶劑及侵蝕性化學物質之抵抗性高。儘管此等膜存在一或多種優勢，但仍需要具有諸如低CWST值及/或對有機溶劑及/或侵蝕性化學物質之抵抗性提高之改良特性的氟聚合物及包含此類氟聚合物之膜。
本發明提供具有低CWST值之氟聚合物及由該等氟聚合物製備之膜。在一具體實例中，本發明提供一種包含式A-X-CH2-B之聚合單體單元之氟聚合物，其中A為C6F13-(CH2)2，X為O或S，且B為乙烯基苯基，且該氟聚合物具有至少100Kd之重量平均分子量(Mw)及/或至少33℃共聚物之玻璃轉移溫度。
氟聚合物為超疏水聚合物且可用於賦予材料表面疏油特性，亦即低至15達因/公分之CWST。本發明亦提供一種製備多孔膜之方法， 該多孔膜包含安置於多孔載體上之共聚物。本發明進一步提供一種將流體，尤其含有氣體溶解或分散其中之流體脫氣的方法。舉例而言，多孔膜適合於移除以低於1ppb或低於大多數儀器之偵測極限之濃度存在於流體中的氣態雜質。
本發明之氟聚合物膜具有以下優勢中之一或多者：具有15-23達因/公分之表面張力之疏油膜由單步塗佈法製備，而不需膜之後處理。由此方法製得之疏油膜對於酸、鹼、氧化劑及/或熱為穩定的。疏油膜保留至少80%之其孔隙率。膜穩定，可耐受15mmHg之真空保持，例如持續15小時或更久。低至0.25%之聚合物濃度能夠產生具有23達因/公分之表面張力值之疏油膜。聚合物塗層可適於塗佈在許多(若非所有)多孔載體膜及薄膜上。因為該方法使用極少修改或無修改之已有機器，所以其不需要對用於澆鑄膜之設備大量投資。本發明提供一種均聚物，該均聚物在塗佈在膜上時具有23達因或更少之表面張力而不需膜之後處理。膜為多孔的，具有高水突破壓力及/或高氣流速率。
【發明詳細說明】
根據一具體實例，本發明提供一種包含下式之聚合單體單元之氟聚合物A-X-CH2-B，其中A為C6F13-(CH2)2，X為O或S，且B為乙烯基苯基，且該氟聚合物具有至少約100Kd之重量平均分子量(Mw)及/或至少約33℃共聚物之玻璃轉移溫度。
根據本發明，B為間乙烯基苯基、對乙烯基苯基或其混合物。舉例而言，氟聚合物包含間-[全氟己基伸乙基硫基甲基]苯乙烯、對-[全氟己基伸乙基硫基甲基]苯乙烯或其混合物作為單體單元。在另一實例中，氟聚合物包含間-[全氟己基伸乙基氧基甲基]苯乙烯、對-[全氟己基伸乙基氧基甲基]苯乙烯或其混合物。
在一具體實例中，氟聚合物具有至少約100Kd、至少約400Kd、至少約600Kd、至少約800Kd或至少約1000Kd之Mw。舉例而言，氟聚合物具有約100Kd至約4000Kd、較佳約500Kd至約1500Kd且更佳約1100Kd至約1300Kd之Mw。
在一具體實例中，氟聚合物具有至少約60Kd、至少約200Kd、至少約400Kd、至少約600Kd或至少約1000Kd之數目平均分子量(Mn)。舉例而言，氟聚合物具有約100Kd至約2000Kd、較佳約200Kd至約1500Kd且更佳約400Kd至約1400Kd，且在另一具體實例中約60Kd至約1200Kd之Mn。
在以上具體實例中之任一者中，氟聚合物具有約1.5至約5、 約1.5至約4或約1.5至約3之多分散性指數(Mw/Mn)。
在一特定具體實例中，氟聚合物具有至少約98Kd之Mw。
單體可藉由使C6F13-(CH2)2-Y與鹵烷基苯乙烯反應來製備，其中Y為SH或OH。
氟聚合物可藉由任何合適方法由單體製備。舉例而言，可使用自由基聚合，尤其藉由使用引發劑與自由基穩定劑之組合。在一具體實例中，氟聚合物可在約130℃至約180℃之溫度下藉由單體之自引發熱聚合製備。
根據一具體實例，使用(2,2,6,6-四甲基哌啶-1-基)氧基(TEMPO)用於聚合允許聚合物鏈之緩慢增長率及較短鏈之再組合，從而產生具有狹窄分子量分佈之聚合物。
單體藉由本文揭示之特殊方法自全氟己基乙基硫醇、全氟己基乙醇或其八碳氟化類似物及氯甲基苯乙烯合成。本文揭示之方法簡化單體及聚合物之合成及純化，使其可用於工業應用。
合成單體及後續聚合物之較佳方法如下：將263mmol氟化硫醇與238mmol當量氯甲基苯乙烯在100mL DMF及33mL 8M氫氧化鈉下混合在500mL圓底燒瓶中。將反應混合物在室溫下攪拌1小時且在分液漏斗中分離。使所得產物在2毫巴(mbar)下於140℃下蒸餾，例如產率為85%。
氟聚合物可溶於鹵化溶劑，如氯仿；二氯甲烷；1,2-二氯乙烷；1,1,1,3,3,3-六氟-2-丙醇；1,1,2-三氯-1,2,2-三氟乙烷及1,1,1,2,2-五氟-3,3-二氯丙烷。然而，此等溶劑中之一些可能有毒或可能不會提供最佳CWST 值。
合適溶劑之實例包括甲氧基丁烷，諸如(CF3)2CF-CF2OCH3、CF3CF2CF2CF2OCH3或其混合物，單獨或與異丙醇(IPA)組合。此類溶劑為環境友好的。此等溶劑中之一些可作為工程溶劑購得，例如Novec 7100TM(甲氧基-九氟丁烷)或NovecTM 71IPA甲氧基-九氟丁烷與IPA之組合，其為環境友好的且危害較小，且為較佳。
使用氟化溶劑或工程溶劑提高氟聚合物與多孔載體之黏著力。
本發明進一步提供一種包含上述氟聚合物之多孔膜，其中該多孔膜係獨立的或安置於多孔載體，例如多孔聚合載體上。
在一具體實例中，多孔聚合載體係選自PVC/PAN、聚碸、聚醯胺、纖維素、聚酯、聚醚碸、聚烯烴，例如聚丙烯或聚乙烯、尤其HDPE、PET、PPS、PPSU(聚苯碸)、PTFE、PVDF、PVF(聚氟乙烯)、PCTFE(聚氯三氟乙烯)、FEP(氟化乙烯-丙烯)、ETFE(聚乙烯四氟乙烯)、ECTFE(聚乙烯氯三氟乙烯)、PFPE(全氟聚醚)、PFSA(全氟磺酸)、全氟聚氧代環丁烷、聚醯亞胺、聚醚醯亞胺、聚碳酸酯及聚苯乙烯。
多孔膜為疏油性的，且在一具體實例中，具有約23達因/公分或更少，例如15-23達因/公分，尤其15達因/公分、16達因/公分、17達因/公分、18達因/公分、19達因/公分、20達因/公分、21達因/公分、22達因/公分及23達因/公分之CWST。
多孔膜可藉由例如利用諸如UV或電子束之聚合輻射使單體在多孔載體上聚合來就地製備。可替代地及較佳地，多孔膜藉由用氟聚 合物之溶液塗佈多孔載體來製備。
膜之CWST可藉由任何合適方法量測。在一具體實例中，方法依賴於一組某種組成之溶液。各溶液具有特定表面張力。溶液之表面張力值以較小非相等增量處於15達因/公分至92達因/公分之範圍內。為量測表面張力，將膜位於白光台之頂部上，將一滴某一表面張力之溶液塗覆於多孔膜表面，且記錄液滴滲透多孔膜且變為亮白色(表明光穿過多孔膜)所花費之時間。當液滴滲透多孔膜所花費之時間10秒時，視為即刻潤濕。產生即刻潤濕之溶液界定多孔膜之CWST。若時間>10秒，則溶液視為將多孔膜部分潤濕。
根據本發明之一具體實例，多孔膜為多孔膜，例如奈米多孔膜，例如孔直徑在1nm與100nm之間的多孔膜或孔直徑在1μm與10μm之間的微孔膜。
本發明之態樣包括但不限於：a)多孔疏油膜，源自利用聚合物聚[對/間-[[(全氟己基伸乙基)硫基]甲基]-苯乙烯及聚[對/間-[[(全氟己基伸乙基)氧基]甲基]-苯乙烯進行單步表面塗佈，且具有在15達因/公分與23達因/公分之間的表面張力；b)具有在15達因/公分與23達因/公分之間的表面張力之多孔疏油膜，源自利用單體全氟己基伸乙基硫基甲基苯乙烯及全氟己基伸乙基氧基甲基苯乙烯進行表面塗佈，且隨後經電子束能量輻射以獲得疏油表面；c)多孔疏油膜，源自利用聚合物聚[對/間-[[(全氟己基伸乙基)硫基]甲基]-苯乙烯及聚[對/間-[[(全氟己基伸乙基)氧基]甲基]-苯乙烯進行 單步表面塗佈且具有在15達因/公分與23達因/公分之間的表面張力，且具有在20℃至150℃範圍內之塗佈後乾燥溫度；及d)經修改之方法，其簡化用於製備對商業及工業應用有用之多孔膜之全氟己基伸乙基硫基甲基苯乙烯的合成及聚[對/間-[[(全氟己基伸乙基)硫基]甲基]-苯乙烯的後續合成。
多孔膜可以許多方式之一包含氟聚合物。舉例而言，多孔膜可包括包含共聚物之塗層。多孔膜可藉由將2%聚合物溶解於合適溶劑，例如丙酮中來製備且將多孔載體，諸如PTFE浸漬於聚合物溶液2秒。經塗佈之載體於烘箱中在80℃下乾燥20分鐘，且產物浸沒於IPA中2小時，於烘箱中在80℃下乾燥30分鐘以獲得多孔膜。PTFE載體及塗佈在該載體上之多孔膜之表面的SEM顯微圖分別描繪於圖1-圖2中。
膜可經旋塗、滴塗、噴塗、浸塗或印刷塗佈。塗佈可在不存在額外熱乾燥之情況下進行。然而，因為例如額外加熱可提高膜之韌性，所以其為較佳。其能夠耐受負壓，例如達至15mm Hg。
根據本發明之具體實例，多孔膜可具有多種組態，包括平面、平板、摺疊、管狀、螺旋形及中空纖維。在一個具體實例中，多孔膜為中空纖維膜。
根據本發明之具體實例之多孔膜典型地安置於包含至少一個入口及至少一個出口且界定入口與出口之間的至少一個流體流動路徑之殼體中，其中至少一個本發明膜或包括至少一個本發明膜之過濾器跨越流體流動路徑，以提供過濾裝置或過濾器模組。在一具體實例中，提供一種過濾裝置，其包含：包含入口及第一出口且界定入口與第一出口之間的第 一流體流動路徑的殼體；及至少一個本發明膜或包含至少一個本發明膜之過濾器，本發明膜或包含至少一個本發明膜之過濾器跨越第一流體流動路徑安置於殼體中。
較佳地，對於交叉流應用，至少一個本發明膜或包含至少一個本發明膜之過濾器安置於包含至少一個入口及至少兩個出口且界定入口與第一出口之間的至少一個第一流體流動路徑及入口與第二出口之間的第二流體流動路徑之殼體中，其中本發明膜或包含至少一個本發明膜之過濾器跨越第一流體流動路徑以提供過濾裝置或過濾器模組。在一說明性具體實例中，過濾裝置構成交叉流過濾模組、殼體，該殼體包含入口、包含濃縮物出口之第一出口及包含滲透物出口之第二出口且界定入口與第一出口之間的第一流體流動路徑及入口與第二出口之間的第二流體流動路徑，其中至少一個本發明膜或包含至少一個本發明膜之過濾器跨越第一流體流動路徑安置。
過濾裝置或模組可滅菌。可採用具有合適形狀且提供一入口及一或多個出口之任何殼體。
殼體可由任何合適剛性不可滲透之材料製造，包括任何不可滲透之熱塑性材料，其與處理中之流體相容。舉例而言，殼體可由以下製造：金屬，諸如不鏽鋼；或聚合物，例如透明或半透明聚合物，諸如丙烯酸樹脂、聚丙烯樹脂、聚苯乙烯樹脂或聚碳酸酯樹脂。
根據本發明之具體實例之多孔膜可用於過濾空氣及/或氣體及/或可用於排氣應用(例如，允許空氣及/或氣體通過但不允許液體通過)。
根據本發明之具體實例之多孔膜亦可用於多種應用中，包括 例如診斷應用(包括例如樣品製備及/或診斷性側流裝置)、噴墨應用、微影術(例如替代基於HD/UHMW PE之介質)、過濾用於醫藥行業之流體、金屬移除、生產超純水、處理工業用水及表層水、過濾用於醫學應用之流體(包括用於家庭及/或患者使用，例如靜脈內應用，亦包括例如，過濾生物流體，諸如血液(例如移除病毒))、過濾用於電子行業之流體(例如過濾微電子行業中之光阻流體及熱SPM)、過濾用於食品及飲料行業之流體、啤酒過濾、澄清、過濾含抗體及/或蛋白質之流體、過濾含核酸之流體、細胞偵測(包括原位)、細胞捕獲及/或過濾細胞培養物流體。根據本發明之具體實例之多孔膜可用於多種裝置中，包括手術裝置及產品，諸如眼科手術產品。脫氣應用之一實例為將靜脈內(IV)流體脫氣。若IV流體在注射前未經適當脫氣，則該IV流體可將氣栓引入循環系統中，此在某些情況下可能致命。
本發明之一個較佳用途係塗佈多孔膜用於生物製藥及醫藥行業中之排氣應用。可替代地，疏油塗層可用於防冰或用於疏冰表面，且可塗佈在纖維玻璃、金屬及鋁表面、電力線、船體及飛機機翼上。
無孔薄膜可使用聚合物聚[對/間-[[(全氟己基伸乙基)硫基]甲基]-苯乙烯及聚[對/間-[[(全氟己基伸乙基)氧基]甲基]-苯乙烯及其高碳氟化類似物塗佈以實現具有高表面能之疏油表面。塗佈可藉由旋塗、滴塗、噴塗、浸塗或印刷塗佈進行。
以下實施例進一步說明本發明，但當然不應解釋為以任何方式限制其範疇。
實施例1
此實施例說明根據本發明之一具體實例之單體之製備。
對-[[(全氟己基伸乙基)硫基]甲基]-苯乙烯(PFOMS)之製備：在3L反應器中將2-全氟己基乙基硫醇(1000g，2.63M)溶解於DMF(1L)中，且以350rpm添加8M NaOH(330mL)水溶液(放熱)，隨後添加乙烯基苯甲基氯(364g，2.39M)。在80℃下攪拌反應混合物15小時。在冷卻後，所得混合物使用2L分液漏斗分離(產物更稠密)。另外用己烷(600mL)萃取H2O/DMF層。合併之有機層用7%碳酸氫鈉水溶液洗滌，且碳酸氫鈉層用己烷(300mL)再萃取。因此獲得之產物進一步用飽和氯化鈉(1L)洗滌，且用無水硫酸鈉脫水。產物經由矽膠(己烷中之750g)過濾，且用己烷(3L)溶離。在濃縮之後，對所獲得之最終產物稱重(1.115kg，2.25M，86%產率)。 1H NMR(以ppm為單位之CDCl3)：δ 2.25(m,2H),2.60(d,2H),3.70(s,2H),5.25(d,1H),5.75(d,1H),6.69(dd,1H),7.25(d,2H),7.40(d,2H)。
實施例2
此實施例說明根據本發明之一具體實例製備氟聚合物聚[對-[[(全氟己基伸乙基)硫基]甲基]苯乙烯](PST-S)。
將對-[[(全氟己基伸乙基)硫基]甲基]-苯乙烯(1.115kg，2.25M)與甲苯(350g)及偶氮二異丁腈(AIBN)(11g，674mmol，3莫耳%)混合在2L燒瓶中，且在0℃下用氮氣脫氣45分鐘。在60℃下攪拌反應混合物14小時。所得產物緩慢沈澱於甲醇(9L)中，歷經2小時，且另外混合1小時。將溶劑傾析且產物再溶解於氯仿(2L)中，且再沈澱於新鮮甲醇(15L)中。在混合5小時之後，產物使用室內真空經由燒結漏斗或濾紙過濾，且用甲醇(500mL)沖洗。使產物在室內真空下乾燥1小時，且在 真空烘箱中隔夜或在30℃直至完全乾燥。所獲得之聚合物重912g，按單體之重量計產率為82%。
實施例3
此實施例說明根據本發明之一具體實例製備另一氟聚合物聚[對-[[(全氟己基伸乙基)氧基]甲基]-苯乙烯]P(PFOMS)。
單體PFOMS(15.2g，31.7mmol)裝入具有2,2′-偶氮二(2-甲基丙腈)(AIBN)(207.7mg，1.23mmol)及四氫呋喃(THF)(7.5g，104mmol)之250mL圓底燒瓶中。在60℃下攪拌12h之後，反應混合物傾入甲醇中，且所獲得之沈澱物藉由自溶劑NovecTM 71IPA之若干次沈澱至甲醇而純化。產率：85%。
表1列出均聚物之玻璃轉移溫度(Tg)。
實施例4
此實施例說明根據本發明之一具體實例之塗佈程序。
將20nm、0.1μm、0.2μm、0.45μm或lμm的熔噴聚酯背襯之PTFE及無載體之PTFE膜切割為5吋×5吋薄片。膜之若干薄片置放於不鏽鋼盤中。將具有在氯仿、NovecTM 71IPA或NovecTM 7100中0.5%、0.75%、1.0%、1.5%、2.0%、2.5%或3.0%之聚合物濃度的塗佈溶液傾入盤中且輕緩震盪以確保膜徹底經塗佈溶液浸沒。將膜樣品自浸泡溶液移除且於烘箱中在80℃下乾燥20分鐘，隨後測試膜效能。下表2展示來自0.2μm聚酯背襯 之PTFE膜之測試結果。
實施例5
此實施例說明根據本發明之一具體實例製備親油膜。
將孔直徑為0.1μm、0.2μm、0.45μm、1μm或5μm之聚酯背襯之聚醚碸(PES)及無載體之PES膜切割為5吋×5吋薄片。此類膜之若干薄片置放於不鏽鋼盤中。將具有在NovecTM 71IPA或NovecTM 7100中0.5%、0.75%、1.0%、1.5%、1.75%、2.0%、2.25%、2.5%或3.0%之聚合物濃度的塗佈溶液傾入盤中且輕緩震盪以確保膜徹底經塗佈溶液浸沒。將膜樣品自浸泡溶液移除且於烘箱中在70℃、80℃、90℃、100℃、120℃或140℃下乾燥20分鐘。下表2-表4闡述在70℃下及在120℃下來自此膜之測試結果。
實施例6
此實施例說明根據本發明之一具體實例自PVDF及耐綸(Nylon)膜製備親油膜。
將0.2μm、0.45μm、1μm或5μm孔直徑的聚酯背襯之PVDF及無載體之耐綸膜或纖維素深度薄片切割為5吋×5吋薄片。膜之若干薄片置放於不鏽鋼盤中。將具有在NovecTM71IPA或NovecTM7100中0.5%、0.75%、1.0%、1.5%、2.0%、2.5%或3.0%之聚合物濃度的塗佈溶液傾入盤中且輕緩 震盪以確保膜徹底經塗佈溶液浸沒。將膜樣品自浸泡溶液移除且於烘箱中在70℃、80℃、90℃、100℃、120℃或140℃下乾燥20分鐘。下表5闡述在70℃下來自此類膜之測試結果。
實施例7
此實施例說明根據本發明之一具體實例自Nylon、HDPE及PTFE膜製備親油膜。
將孔直徑5nm耐綸膜、5nm及10nmPTFE膜及5nm及10nm HDPE膜切割為5吋×5吋薄片。膜之若干薄片置放於不鏽鋼盤中。將具有在NovecTM 7100中0.4%之聚合物濃度的塗佈溶液傾入盤中且輕緩震盪10秒。 將膜樣品自浸泡溶液移除且於烘箱中在130℃下乾燥20分鐘。
本文中所引用之所有參考文獻，包括公開案、專利申請案及專利均以引用之方式併入本文中，其引用程度就如同個別及特定地指示各參考文獻以引用之方式併入且全文闡述於本文中一般。
除非本文中另外指示或與上下文明顯矛盾，否則在描述本發 明之上下文中(尤其在以下申請專利範圍之上下文中)，應將術語「一(a/an)」及「該(the)」及「至少一個(at least one)」及類似涉及對象之使用解釋為涵蓋單數與複數兩者。除非本文另外指示或與上下文明顯矛盾，否則使用術語「至少一個」後接一或多個項目之清單(例如「A及B中之至少一者(at least one of A and B)」)應解釋為意謂選自所列舉項目之一個項目(A或B)或所列舉項目之兩個或超過兩個之任何組合(A及B)。除非另外指出，否則術語「包含(comprising)」、「具有(having)」、「包括(including)」及「含有(containing)」應解釋為開放式術語(亦即，意謂「包括但不限於，(including,but not limited to,)」)。除非本文另外指示，否則本文中數值範圍之敍述僅意欲充當個別提及屬於該範圍內之各獨立值之速記方法，且各獨立值併入本說明書中，如同在本文中個別敍述一般。除非本文另外指示或另外與上下文明顯矛盾，否則本文所述之所有方法可以任何適合順序進行。除非另外主張，否則使用本文所提供之任何及所有實例或例示性語言(例如「諸如」)僅意欲更好地闡明本發明而非對本發明之範圍造成限制。本說明書中之語言不應理解為指示實施本發明所必需之任何未主張要素。
本文描述本發明之較佳具體實例，其包括本發明者已知用於進行本發明之最佳模式。在閱讀前文描述之後，彼等較佳具體實例之變化對於一般技術者而言可變得顯而易見。本發明人期望熟習此項技術者適當時採用此類變化，且本發明人意欲以不同於本文中特定描述之其他方式來實施本發明。因此，在適用法律允許下，本發明包括隨附於本文之申請專利範圍中所敍述之主題的所有修改及同等物。此外，除非本文另外指示或另外與上下文明顯矛盾，否則本發明涵蓋上述要素呈其所有可能變化形式 之任何組合。
圖1A描繪根據本發明之一具體實例之氟聚合物膜上的一滴水之接觸角。圖1B描繪根據本發明之一具體實例之氟聚合物膜上的一滴IPA之接觸角。
圖2A描繪根據本發明之一具體實例之氟聚合物膜上的一滴水之接觸角。圖2B描繪根據本發明之一具體實例之氟聚合物膜上的一滴IPA之接觸角。

Claims (18)

  1. 一種包含下式之聚合單體單元之氟聚合物，A-X-CH 2-B，其中A為C 6F 13-(CH 2) 2，X為O或S，且B為乙烯基苯基，且該氟聚合物具有至少100Kd之重量平均分子量(Mw)及/或至少約33℃共聚物之玻璃轉移溫度。
  2. 如申請專利範圍第1項之氟聚合物，其中B為間乙烯基苯基、對乙烯基苯基或其混合物。
  3. 如申請專利範圍第1項或第2項之氟聚合物，其中該單體單元為間-[全氟己基伸乙基硫基甲基]苯乙烯、對-[全氟己基伸乙基硫基甲基]苯乙烯或其混合物。
  4. 如申請專利範圍第1項或第2項之氟聚合物，其中該單體單元為間-[全氟己基伸乙基氧基甲基]苯乙烯、對-[全氟己基伸乙基氧基甲基]苯乙烯或其混合物。
  5. 如申請專利範圍第1項至第4項中任一項之氟聚合物，其中該氟聚合物具有至少200Kd之Mw。
  6. 如申請專利範圍第1項至第5項中任一項之氟聚合物，其中該氟聚合物具有400Kd至1300Kd之Mw。
  7. 如申請專利範圍第1項至第6項中任一項之氟聚合物，其中該氟聚合物具有1100Kd至1300Kd之Mw。
  8. 一種多孔膜，其包含如申請專利範圍第1項至第7項中任一項之氟聚合物。
  9. 如申請專利範圍第8項之多孔膜，該多孔膜包括多孔載體。
  10. 如申請專利範圍第9項之多孔膜，其中該多孔載體為多孔聚合載體。
  11. 如申請專利範圍第10項之多孔膜，其中該多孔聚合載體係選自PVC/PAN、聚碸、聚醯胺、纖維素、聚酯、聚醚碸、聚烯烴、PET、PPS、PPSU(聚苯碸)、PTFE、PVDF、PVF(聚氟乙烯)、PCTFE(聚氯三氟乙烯)、FEP(氟化乙烯-丙烯)、ETFE(聚乙烯四氟乙烯)、ECTFE(聚乙烯氯三氟乙烯)、PFPE(全氟聚醚)、PFSA(全氟磺酸)、全氟聚氧代環丁烷、聚醯亞胺、聚醚醯亞胺、聚碳酸酯及聚苯乙烯。
  12. 一種製備包含如申請專利範圍第1項至第7項中任一項之氟聚合物之多孔膜的方法，該方法包含：(i)使該氟聚合物溶解於溶劑或溶劑之混合物中以獲得包含該氟聚合物之溶液；(ii)將來自(i)之該溶液塗佈在多孔載體上；及(iii)使該溶劑或溶劑之混合物自該塗層蒸發以獲得該多孔膜。
  13. 如申請專利範圍第12項之方法，其中該溶劑或溶劑之混合物包含鹵化溶劑，視情況與醇組合。
  14. 如申請專利範圍第13項之方法，其中該溶劑或溶劑之混合物係選自甲氧基九氟丁烷、甲氧基九氟丁烷、氯仿、二氯甲烷、1,2-二氯乙烷；1,1,2-三氯-1,2,2-三氟乙烷、1,1,1,2,2-五氟-3,3-二氯丙烷，視情況與異丙醇及/或1,1,1,3,3,3-六氟-2-丙醇組合。
  15. 一種多孔膜，其藉由如申請專利範圍第12項至第14項中任一項之方法製備。
  16. 如申請專利範圍第8項至第11項或第15項中任一項之多孔膜，該多孔膜具有15達因/公分至23達因/公分之CWST。
  17. 一種過濾流體之方法，該方法包含使該流體通過如申請專利範圍第8項至第11項、第15項或第16項中任一項之多孔膜。
  18. 如申請專利範圍第17項之方法，其中存在於該流體中之氣體自該流體移除。
TW106126566A 2016-09-16 2017-08-07 氟聚合物及包含氟聚合物（iii）的膜 TWI648295B (zh)

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Publication number Priority date Publication date Assignee Title
CN113786743B (zh) * 2021-09-28 2023-07-18 常熟三爱富中昊化工新材料有限公司 气体分离膜、其制备方法和用途

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3380983A (en) * 1965-04-28 1968-04-30 Texaco Inc Fluorocarbon derivative of polystyrene and process of preparing same
JPS61293943A (ja) * 1985-06-18 1986-12-24 Sagami Chem Res Center 含フッ素スチレン誘導体
JPS6397215A (ja) 1986-10-15 1988-04-27 Sagami Chem Res Center 気体透過性重合体膜
US4954256A (en) 1989-05-15 1990-09-04 Pall Corporation Hydrophobic membranes
US5834523A (en) * 1993-09-21 1998-11-10 Ballard Power Systems, Inc. Substituted α,β,β-trifluorostyrene-based composite membranes
JP4080565B2 (ja) * 1996-04-26 2008-04-23 大日本インキ化学工業株式会社 多孔質体の製造方法および多孔質体
JP2002540928A (ja) 1999-04-14 2002-12-03 ポール・コーポレーション 多孔質膜
KR100370399B1 (ko) * 2000-06-30 2003-01-29 삼성전자 주식회사 트리플루오로스티렌과 치환된 비닐 화합물을 기초로 한부분불소화된 공중합체 및 이로부터 형성된 이온 전도성고분자막
JP2009245979A (ja) 2008-03-28 2009-10-22 Fujitsu Ltd 半導体装置およびその製造方法
US20090277837A1 (en) 2008-05-06 2009-11-12 Chunqing Liu Fluoropolymer Coated Membranes
US9290596B2 (en) * 2010-05-27 2016-03-22 The Chemours Company Fc, Llc Solvent-based fluoropolymer additives and their use in coating compositions
EP2586805A4 (en) 2010-06-23 2015-09-30 Asahi Glass Co Ltd Heatable Composition and Method of Making a Hardened Film
US8940846B2 (en) * 2010-07-01 2015-01-27 Solvay Specialty Polymers Italy S.P.A. Process for the treatment of sulfonyl fluoride polymers
JP5459554B2 (ja) 2010-09-15 2014-04-02 株式会社リコー センサデバイス
CN102649028A (zh) * 2011-02-25 2012-08-29 天津工业大学 一种疏水性分离膜以及制备方法
JP4979824B1 (ja) 2011-03-29 2012-07-18 株式会社アストム イオン交換膜
US8758491B2 (en) * 2011-06-17 2014-06-24 Honeywell International Inc. Thin film gas separation membranes
CN102698618B (zh) * 2012-04-16 2015-11-18 中国科学院过程工程研究所 一种用于膜蒸馏过程的聚醚砜多孔膜及其制备方法
KR101883130B1 (ko) * 2012-12-20 2018-07-27 미쯔비시 케미컬 주식회사 중합체 조성물 및 다공질막
US9604157B2 (en) * 2013-03-12 2017-03-28 Aperia Technologies, Inc. Pump with water management
JP2015042621A (ja) * 2013-08-26 2015-03-05 東レ・ファインケミカル株式会社 ビニルベンジル（フルオロアルキル）エーテルの製造方法
US9604181B2 (en) 2014-05-30 2017-03-28 Pall Corporation Membrane comprising self-assembled block copolymer and process for producing the same by spray coating (IIc)
US9962662B2 (en) 2014-06-30 2018-05-08 Pall Corporation Fluorinated polymer and use thereof in the preparation of hydrophilic membranes (vi)
JP2016137455A (ja) 2015-01-28 2016-08-04 富士フイルム株式会社 複合イオン交換膜及びその製造方法、イオン交換膜モジュール、並びに、イオン交換装置
US10471396B2 (en) * 2016-08-15 2019-11-12 Pall Corporation Fluoropolymers and membranes comprising fluoropolymers (I)
US10576431B2 (en) * 2016-08-15 2020-03-03 Pall Corporation Fluoropolymers and membranes comprising fluoropolymers (II)

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